CN107372496B - Application of phenylhydrazino ketone compound as agricultural bactericide - Google Patents
Application of phenylhydrazino ketone compound as agricultural bactericide Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
- A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/48—Nitro-carboxylic acids; Derivatives thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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Abstract
The invention relates to application of a phenylhydrazino ketone compound as an agricultural bactericide. The application of the phenylhydrazino ketone compound shown in the formula (1) in inhibiting or killing fungi causing crop diseases and the application of the phenylhydrazino ketone compound as an agricultural bactericide have the advantage of high activity when being used for inhibiting the growth of the fungi causing the crop diseases, and are suitable for preventing and treating the plant diseases caused by the fungi. Can be used for preventing and treating diseases caused by various fungi including rice blast and wheat scab.
Wherein: r1,R2,R3,R4,R5Each independently selected from hydrogen, halogen, alkyl, alkoxy, hydroxyl, cyano, trifluoromethyl, sulfonamide and nitro; r6Selected from hydrogen, halogen, alkyl, amino, cyano, CH3CH2S‑、CH3CO‑、CF3CH2CO-or CF3CO‑、
R7Alkyl, hydroxyl, phenyl, halogenated phenyl, alkoxy and trifluoromethyl; x may be nitrogen or carbon, and when X is nitrogen, R5Is absent.
Description
Technical Field
The invention relates to the field of pesticides, in particular to application of a phenylhydrazino ketone compound in inhibiting or killing fungi causing crop diseases and application of the phenylhydrazino ketone compound as an agricultural bactericide for treating diseases caused by the fungi of crops by inhibiting or killing pathogenic bacteria.
Background
With the increasing population, the demand of food is gradually increased, and the improvement of the yield of food is an urgent and severe task in the face of the loss of cultivated land, the shortage of water resources and the increasing demand of food. Grain crops such as rice and wheat are one of the most important crops in the world, have wide coverage area and play an important role in human life. For some developing countries, rice, wheat, etc. are the major food and economic sources and are important commercial crops.
Rice blast and wheat scab are important diseases which harm rice and wheat and can cause serious yield reduction of rice and wheat. In order to reduce this loss, pesticides are used appropriately and exert some effect in controlling pests. However, the traditional pesticide has certain defects, because the drug resistance of pests and pathogenic bacteria can be generated by singly using one pesticide for a long time, the pesticide effect is reduced, and a plurality of pesticides have certain destructive effect on the ecological environment. Therefore, in order to solve the above problems, it is urgent to find an effective and environmentally friendly high-efficiency bactericide.
Disclosure of Invention
The invention aims to provide the application of the phenylhydrazino ketone compound in inhibiting or killing fungi causing crop diseases and the application of the phenylhydrazino ketone compound as an agricultural bactericide, wherein the phenylhydrazino ketone compound has the advantage of high activity when being used for inhibiting the growth of the fungi causing the crop diseases and is suitable for preventing and treating plant diseases caused by the fungi. Can be used for preventing and treating diseases caused by various fungi including rice blast and wheat scab.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides the use of a phenylhydrazino ketone compound represented by formula (1) for inhibiting or killing fungi causing crop diseases,
wherein: r1,R2,R3,R4,R5Each independently selected from hydrogen, halogen, alkyl, alkoxy, hydroxyl, cyano, trifluoromethyl, sulfonamide and nitro; r6Selected from hydrogen, halogen, alkyl, amino, cyano, CH3CH2S-、CH3CO-、CF3CH2CO-or CF3CO-、
R7Alkyl, hydroxyl, phenyl, halogenated phenyl, alkoxy and trifluoromethyl;
x may be nitrogen or carbon, and when X is nitrogen, R5Is absent.
According to the scheme, the alkyl comprises a straight-chain alkyl group with 1-18 carbon atoms and a branched-chain alkyl group with 3-18 carbon atoms; the alkoxy group includes a linear alkoxy group having 1 to 18 carbon atoms and a branched alkoxy group having 3 to 18 carbon atoms.
According to the above scheme, R is particularly preferred1Selected from hydrogen, hydroxy, halogen, methyl, cyano, trifluoromethyl, methoxy; r2Selected from hydrogen, halogen; r3Selected from hydrogen, nitro, halogen, sulfonamide, hydroxy; r4Selected from hydrogen, nitro, halogen; r5 is selected from hydrogen; r6Selected from hydrogen, halogen, alkyl, amino, cyano, CH3CH2S-、CH3CO-、CF3CH2CO-or CF3CO-、
R7Is alkyl, hydroxyl, phenyl, halogenated phenyl, alkoxy, trifluoromethyl;
x may be nitrogen or carbon, and when X is nitrogen, R5Is absent.
According to the scheme, the phenylhydrazino ketone compound is selected from target compounds shown in the following table:
according to the scheme, the fungi include but are not limited to rice blast fungus, rhizoctonia solani, wheat scab fungus and apple ring rot fungus.
According to the scheme, the crop diseases comprise rice blast, rice sheath blight, wheat scab and apple ring rot.
The reaction synthesis route of the phenylhydrazino ketone compound shown in the formula (1) is as follows:
R1,R2,R3,R4,R5,R4,R5x substituentThe selection of (2) is the same as described above.
In a second aspect, the invention provides an application of a phenylhydrazino ketone compound shown in a formula (1) as an agricultural bactericide,
according to the scheme, the phenylhydrazino ketone compound shown in the formula (1) is used as an active ingredient of an agricultural bactericide, namely, at least one phenylhydrazino ketone compound shown in the formula (1) is used as the active ingredient of the bactericide, and the content of the active ingredient is 0.1-100% based on the total weight of the bactericide.
According to the scheme, when the phenylhydrazinoketone compound shown in the formula (1) is used as an active ingredient of a bactericide, the compound can be prepared into various commonly used dosage forms including but not limited to hydrating agents, emulsions, water solvents, flowable agents and the like by mixing with acceptable carriers or diluents and surface active agents in water, and can be used as the bactericide.
The invention has the beneficial effects that:
the phenylhydrazino ketone compound shown in the formula (1) has the advantages of high inhibition rate and wider bactericidal spectrum when inhibiting the growth of fungi causing crop diseases. The phenylhydrazino ketone compound shown in the formula (1) can be used as an effective component of a bactericide, and can show high-efficiency and remarkable effects when being applied to the comprehensive control of crop diseases caused by fungi including rice blast, rice sheath blight, wheat scab and apple ring rot.
Detailed Description
This patent refers to all the compounds prepared by the following references:
(1)Balkis AL-Saleh,Noha M.Hilmy,Morsy Ahmed EL-Apasery and Mohamed H.Elnagdi,Microwaves in Organic Synthesis:Synthesis of Pyridazinones,Phthalazinones and Pyridopyridazinones from 2-Oxo-Arylhydrazones Under Microwave Irradiation.J.Heterocyclic Chem.,2006,43:1575-1580
(2)Nouria A.Al-Awadi,*Maher R.Ibrahim,a Alya M.Al-Etaibi,and Mohamed H.Elnagdi,Improved synthesis of 2-arylhydrazono-3-hydroxy-1-propanones and their utility in efficient synthesis of pyridazine derivatives,ARKIVOC 2011,2:310-321.
the preparation of the compound of formula (1) of the present invention is specifically described below by way of example 1.
Example 1
Compound WL 201701: preparation of 1- (2- (4-nitrophenyl) hydrazono) propan-2-one
10mmol of ethyl acetoacetate were weighed into a 250ml eggplant-shaped bottle, magnetons were added, an aqueous solution of KOH (3.5g,100ml of water) was added to the eggplant-shaped bottle, and the mixture was stirred at room temperature for 24 hours. Cooled to 0 ℃ and 4.5ml of concentrated HCl, 15ml of ice water are slowly added. Weighing 10mmol of paranitroaniline and 100ml of a two-neck flask, adding magnetons, adding 10ml of water and 3ml of concentrated hydrochloric acid, cooling to 0 ℃, and stirring for 30 min. Slowly add 10mmol NaNo2Stirring the aqueous solution at a temperature of not more than 5 deg.C for 30 min. The diazonium salt just prepared was added dropwise to a 250ml eggplant-shaped flask again, the temperature was maintained at 0-5 ℃ and the solution turned to an orange turbid solution, an aqueous solution of CH3COONa (8.2g,100ml of ice water) was added thereto and stirred at 0-5 ℃ for 2 h. The reaction was nearly complete, and the reaction was allowed to stand to precipitate a solid which was then filtered off to give a yellow solid.
The molecular formula is as follows: c9H9N3O3
1H NMR(600MHz,dmso)δ10.56(s,1H),8.19-8.17(d,2H),7.41(s,1H),7.31-7.30(d,2H),2.36(s,3H).
Yield: 79 percent
The compounds described in this patent are all prepared analogously to compound WF1
Compound WL 201702: 1- (2- (4-bromophenyl) hydrazono) propan-2-one
The molecular formula is as follows: c9H9N2OBr
1H NMR(600MHz,DMSO)δ10.576(s,1H),9.36(d,1H),7.51-7.49(d,2H),7.35-7.33(d,1H),1.94(s,3H).
Yield: 75 percent of
Compound WL 201703: 1- (2- (4-chlorophenyl) hydrazono) propan-2-one
The molecular formula is as follows: c9H9N2OCl
1H NMR(600MHz,DMSO)δ10.57(s,1H),9.37(d,1H),7.40-7.39(d,2H),7.38-7.36(d,1H),1.94(s,3H).
Yield: 68 percent of
Compound WL 201704: 1- (2- (4-nitrophenyl) hydrazono) acetophenone
The molecular formula is as follows: c14H11N3O3
1H NMR(600MHz,DMSO)δ8.26(d,2H),8.03(d,2H),7.88(d,1H),7.65(d,2H),7.55(t,2H),7.40(d,2H).
Yield: 57 percent
Compound WL 201705: 1- (2- (4-nitrophenyl) hydrazono) -4-bromo-acetophenone
The molecular formula is as follows: c14H10BrN3O3
1H NMR(600MHz,DMSO)δ12.01(s,1H),8.19(d,2H),7.91(d,2H),7.77(d,2H),7.45(s,1H),7.20(d,2H).
Yield: 50 percent of
Compound WL 201706: 1- (2- (4-nitrophenyl) hydrazono) butan-2-one
The molecular formula is as follows: c10H11N3O3
1H NMR(600MHz,DMSO)δ11.56(s,1H),8.18-8.17(d,1H),7.43(s,1H),7.30-7.29(d,2H),2.86-2.83(q,2H),1.05-1.03(s,3H).
Yield: 75 percent of
Compound WL 201707: 1- (2- (4-nitrophenyl) hydrazono) butan-2-one
The molecular formula is as follows: c10H11N3O3
1H NMR(600MHz,DMSO)δ11.56(s,1H),8.18-8.17(d,1H),7.43(s,1H),7.30-7.29(d,2H),2.86-2.83(q,2H),1.05-1.03(s,3H).
Yield: 53 percent
Compound WL 201708: 3, 3-dimethyl-1- (2- (4-nitrophenyl) hydrazono) butan-2-one
The molecular formula is as follows: c12H15N3O3
1H NMR(600MHz,DMSO)δ11.85(s,1H),8.21-8.20(d,2H),7.31(s,1H),7.28-7.27(d,2H),7.27(s,1H),1.09(s,6H).
Yield: 77 percent
Compound WL 201709: 1- (2- (3-chlorophenyl) hydrazono) propan-2-one
The molecular formula is as follows: c9H9N2OCl
1H NMR(600MHz,dmso)δ11.40(s,1H),7.34-7.31(d,1H),7.26(s,1H),7.20(s,1H),7.10-7.09(d,1H),6.99-6.91(d,1H),2.33(s,3H).
Yield: 75 percent of
Compound WL 201710: 1- (2- (3, 4-dichlorophenyl) hydrazono) propan-2-one
The molecular formula is as follows: c9H8N2OCl2
1H NMR(600MHz,DMSO)δ11.41(s,1H),753-7.51(d,1H),7.32(d,1H),7.24(d,1H),7.11-7.09(d,1H),2.33(s,3H).
Yield: 70 percent of
Compound WL 201711: 1- (2- (3-nitrophenyl) hydrazono) propan-2-one
The molecular formula is as follows: c9H9N3O3
1H NMR(600MHz,DMSO)δ11.61(s,1H),7.88(s,1H),7.75-7.74(d,1H),7.57-7.54(d,1H),7.27(s,1H),2.34(s,3H).
Yield: 71 percent of
Compound WL 201712: n- (4-nitrophenyl) -2-oxopropanesulfonylhydrazono chloride
The molecular formula is as follows: c9H80N3O3Cl
1H NMR(600MHz,DMSO)δ11.22(s,1H),8.24-8.22(d,2H),7.60-7.59(d,2H),2.55(s,3H).
Yield: 68 percent of
Compound WL201713 ethyl 2- (2- (4-chlorophenyl) hydrazono) acetate
The molecular formula is as follows: c10H11ClN2O2
1H NMR(600MHz,DMSO)δ11.34(s,1H),7.33(d,2H),7.20(d,1H),4.19(d,2H),1.25(t,3H).
Yield: 70 percent of
Compound WL201714 1- (2- (5-chloropyridin-2-yl) hydrazono) propan-2-one
The molecular formula is as follows: c8H8ClN3O
1H NMR(600MHz,DMSO)δ11.15(s,1H),9.37(d,1H),8.31(d,1H),7.88(d,1H),7.41(d,2H),1.96(s,3H).
Yield: 35 percent of
Compound WL 201715-1- (2- (2-chloro-5-nitrophenyl) hydrazono) propan-2-one
The molecular formula is as follows: c9H8ClN3O3
1H NMR(600MHz,DMSO)δ8.22(s,1H),7.78(d,2H),7.72(d,1H),2.39(s,3H).
Yield: 67 percent
Compound WL 201716: 1- (2- (2-methyl-4-chlorophenyl) hydrazono) propan-2-one
The molecular formula is as follows: c10H11ClN2O
1H NMR(600MHz,DMSO)δ10.86(s,1H),7.57(s,1H),7.39(d,1H),7.17(d,2H),2.28(s,3H),2.24(s,3H).
Yield: 63 percent of
Compound WL 201717: 1- (2-phenylhydrazono) propan-2-one
The molecular formula is as follows: c9H10N2O
1H NMR(600MHz,DMSO)δ11.32(s,1H),7.32(t,2H),7.25(s,1H),7.19(d,2H),6.96(t,1H),2.32(s,3H).
Yield: 72 percent
Compound WL 201718: n- (3, 4-dichlorophenyl) -2-oxopropanesulfonazinylidene chloride
The molecular formula is as follows: c9H7Cl3N2O
1H NMR(600MHz,DMSOδ10.92(s,1H),7.62(d,1H),7.54(d,1H),7.41(dd,1H),2.48(s,4H).
Yield: 57 percent
Compound WL 201719: 2- (2- (3-chlorophenyl) hydrazono) -5, 5, 5-trifluoro-1-phenylpentane-1-3-dione
The molecular formula is as follows: c17H12ClF3N2O2
1H NMR(600MHz,DMSO)δ11.76(s,1H),8.15(s,1H),7.79(s,4H),7.71(s,1H),7.58(s,3H),2.54(s,2H).
Yield: 88 percent
Compound WL 201720: 3- (4-nitrophenyl) hydrazono) -1,1, 1-trifluoropentyl-2, 4-dione
The molecular formula is as follows: c11H5F6N3O4
1H NMR(600MHz,DMSO)δ14.25(s,1H),8.32(d,1H),8.09(d,1H),7.82(d,1H),7.55(d,1H).
Compound WL201721 ethyl 4,4, 4-trifluoro-2- (2- (4-nitrophenyl) hydrazono) -3-oxobutyrate
1H NMR(600MHz,DMSO)δ12.87(s,1H),8.32(d,2H),7.69(d,2H),4.40(q,2H),1.35(t,3H).
The molecular formula is as follows: c12H10N3O5F3
Yield: 68 percent of
The compound WL201722:1,1, 1-trifluoro-3- (2- (4-nitrophenyl) hydrazono) pentyl-2, 4-dione
The molecular formula is as follows: c11H8N3O4F3
1H NMR(600MHz,DMSO)δ14.25(s,1H,N-H),8.33(d,J＝9.0Hz,2H,Ar-H),7.80(d,J＝9.0Hz,2H,Ar-H),2.56(s,3H,CH3).
Yield: 73 percent
Compound WL 201723: 1,1, 1-trifluoro-3- (2- (3-nitrophenyl) hydrazono) pentyl-2, 4-dione
The molecular formula is as follows: c11H8N3O4F3
1H NMR(600MHz,DMSO)δ14.32(s,1H),8.51(t,1H),8.06(dd,1H),8.02(dd,1H),7.74(t,1H),2.56(s,3H).
Yield: 74 percent
Compound WL 201724: 3- (2- (5-chloro-2-hydroxyphenyl) hydrazono) -1,1, 1-trifluoropentanyl-2, 4-dione
The molecular formula is as follows: c11H8N3O3F3Cl
1H NMR(600MHz,DMSO)δ14.79(s,1H),7.89(d,1H),7.76(s,1H),7.63(d,1H),2.56(s,3H).
Yield: 71 percent of
The compound WL201725:3- (2- (3-chlorophenyl) hydrazono-pentyl-2, 4-dione
The molecular formula is as follows: c11H11N2O2Cl
1H NMR(600MHz,DMSO)δ13.67(s,1H),7.62(d,1H),7.51(t,1H),7.43(d,1H),7.21(d,1H),2.48(s,3H),2.41(s,3H).
Yield: 82 percent of
Compound WL201726 (2- (2, 4-dioxopent-3-ylidene) hydrazino) benzenesulfonamide
The molecular formula is as follows: c11H13N3O4S
1H NMR(600MHz,DMSO)δ13.70(s,1H),7.86(d,2H),7.72(d,2H),7.37(s,2H),2.49(s,3H),2.45(s,3H).
Yield: 71 percent of
Compound WL 201727: 3- (2- (4-bromophenyl) hydrazono-pentyl-2, 4-dione
The molecular formula is as follows: c11H11N2O2Br
1H NMR(600MHz,DMSO)δ13.85(s,1H),7.59(d,2H),7.53(d,2H),2.47(s,3H),2.41(s,H).
Yield: 80 percent of
Compound WL201728 3- (2- (4-hydroxyphenyl) hydrazono-pentyl-2, 4-dione
The molecular formula is as follows: c11H12N2O3
1H NMR(600MHz,DMSO)δ14.51(s,1H),9.66(s,1H),7.42(d,2H),6.83(d,2H),2.45(s,3H),2.36(s,3H).
Yield: 78 percent of
Compound WL 201729: 3- (2- (2-cyano-4-nitro) phenyl) hydrazono) pentyl-2, 4-dione
The molecular formula is as follows: c12H10N4O4
1H NMR(600MHz,CDCl3)δ14.69(s,1H),8.34(d,1H),8.23(dd,1H),7.91(d,1H),2.66(s,3H),2.56(s,3H).
Yield: 78 percent of
Compound WL 201730: preparation of 3- (2- (4-nitro-2- (trifluoromethyl) phenyl) hydrazono) pentyl-2, 4-dione
The molecular formula is as follows: c12H10F3N3O4
1H NMR(600MHz,CDCl3)δ14.95(s,1H),8.56(s,1H),8.48(d,1H),8.12(d,1H),2.66(d,3H),2.57(d,3H).
Yield: 72 percent
Compound WL 201731: 3- (2- (2-chloro-4-nitrophenyl) hydrazono) pentyl-2, 4-dione
The molecular formula is as follows: c11H10N3O4Cl
1H NMR(600MHz,CDCl3)δ14.62(s,1H),8.28(s,2H),2.65(s,3H),2.48(s,3H).
Yield: 73 percent
Compound WL 201732: 2- (2- (2-hydroxy-5-nitrophenyl) hydrazono) acetic acid ethyl ester
The molecular formula is as follows: c10H11N3O5
1H NMR(600MHz,DMSO)δ11.61(s,1H),11.10(s,1H),8.06(s,1H),7.77(s,1H),7.63(s,1H),7.00(s,1H),4.22(s,2H),1.27(s,3H).
Yield: 61 percent of
Compound WL201733, 2- (2- (2-hydroxy-5-nitrophenyl) hydrazono) acetic acid
The molecular formula is as follows: c8H7N3O5
1H NMR(600MHz,DMSO)δ11.58(s,1H),10.99(s,1H),8.16(s,1H),7.76(s,1H),7.58(s,1H),6.99(s,1H).
Yield: 57 percent
Compound WL 201734: n- (3-nitrophenyl) -2-oxopropanesulfonylhydrazono chloride
The molecular formula is as follows: c11H10N2OCl
The source is as follows: purchase in a commercial databasehttp://www.specs.net
Compound WL 201735: n-phenyl-2-oxopropanesulfonylhydrazono chloride
The molecular formula is as follows: c9H9N2OCl
The source is as follows: purchase in a commercial databasehttp://www.specs.net
Compound WL 201736: n- (4-bromophenyl) -2-oxopropanesulfonylhydrazono chloride
The molecular formula is as follows: c9H8N2OClBr
The source is as follows: purchase in a commercial databasehttp://www.specs.net
Compound WL 201737: n- (2, 4-dichlorophenyl) -2-oxopropanesulfonazinylidene chloride
The molecular formula is as follows: c9H7N2OCl3
The source is as follows: purchase in a commercial databasehttp://www.specs.net
Compound WL 201738: n- (2-chlorophenyl) -2-oxypropylhydrazone phosphorothioate
The molecular formula is as follows: c11H13N2OSCl
The source is as follows: purchase in a commercial databasehttp://www.specs.net
Compound WL 201739: n- (2-chlorophenyl) -2-oxopropionylhydrazone cyanide
The molecular formula is as follows: c10H8N3OCl
The source is as follows: purchase in a commercial databasehttp://www.specs.net
Compound WL 201740: 1- (2- (4-chlorophenyl) hydrazono-1- (piperidine) -1-yl) propan-2-one
The molecular formula is as follows: c14H18N3OCl
The source is as follows: purchase in a commercial databasehttp://www.specs.net
Compound WL 201741: 1-morpholino-1- (2-phenylhydrazono) propan-2-one
The molecular formula is as follows: c13H17N3O2
The source is as follows: purchase in a commercial databasehttp://www.specs.net
Compound WL 201742: n- (3-chlorophenyl) -2-oxopropionylhydrazone amides
The molecular formula is as follows: c9H10N3OCl
The source is as follows: purchase in a commercial databasehttp://www.specs.net
Example 2
Determination of bactericidal activity of phenylhydrazino ketone compound on plant pathogenic fungi
Experimental Material
Magnaporthe grisea, Rhizoctonia solani, Gibberella tritici, and Rhizopus malorum
DMSO
The PDA culture medium formula comprises: cleaning fresh potato, peeling, weighing 200g, cutting into pieces, adding into appropriate amount of sterile water, cooking with electromagnetic oven (boiling water, further cooking for 20-30min), filtering with gauze twice when the temperature of culture medium is reduced, and filtering to remove solid potato to obtain potato liquid of about 1L. And finally adding 20g of glucose and 18-20g of agar powder into the potato liquid. Subpackaging with conical flasks, sterilizing at 121 ℃ for 20 minutes, and cooling to about 55 ℃ for later use.
Preparation of the medicament:
weighing a proper amount of m mg of the drug to be detected, and diluting the drug with 10m microliter DMSO to obtain mother liquor. According to the activity of the medicament, 6-10 series of mass concentrations are set, and the final content of the organic solvent is not more than 2%.
Medicament treatment:
under the condition of aseptic operation, taking a conical flask filled with PDA culture medium in advance, quantitatively sucking liquid medicine from low concentration to high concentration in sequence, adding into the conical flasks respectively, and shaking up sufficiently. Pouring into 3 sterilized and dried culture dishes with diameter of 9mm to obtain flat plates containing medicine.
The experiment was run with treatment without agent as a blank.
Inoculation:
under aseptic condition, cutting off multiple pieces of culture medium (i.e. cake) with diameter of 0.5cm from the edge of cultured pathogenic bacteria with a puncher, inoculating the cake onto solidified solid culture medium containing compound in a culture dish with an inoculating needle, and tightly attaching the mycelium to the culture medium. The dish is covered and sealed by a sealing film. The cells were incubated at 28 ℃ in an incubator.
And (3) data measurement:
according to the growth of pathogenic bacteria in the culture dish of the blank control. The colony diameter was measured in millimeters (mm) with a caliper. The diameter of each colony was measured by the cross method, and the average value was taken.
Data processing:
the calculation method of the bacteriostatic rate is shown as a formula 5-1 and a formula 5-2:
pure growth (mm) ═ colony diameter-cake diameter
The bacteriostasis rate is (CK pure growth amount-treated pure growth amount)/CK pure growth amount is 100 percent
The inhibition rate is directly calculated according to the formula
Calculation of EC 50: the hypha growth inhibition rate is y, the medicament concentration (mu g/m L) is x, a logistic regression equation is used for fitting, and the effective middle concentration (EC50) of the bactericide for inhibiting the hypha growth of rice blast fungus is calculated, so that the strength of the bactericide for inhibiting the rice blast fungus is shown.
Experimental methods
Experimental results and analysis:
the result of the determination of the inhibitory activity of the phenylhydrazino ketone compound on the plant pathogenic fungi is shown in the table I, and the result of the table I shows that the phenylhydrazino ketone compound has better inhibitory action on rice blast, rice sheath blight pathogenic bacteria and wheat gibberella.
In addition, the invention lists the toxicity of some phenylhydrazino ketone compounds on rice blast germs, and the results are shown in the second table. The magnitude of the EC50 value of the medicament is an important index for measuring the magnitude of the toxicity of the medicament, and the smaller the EC50 value is, the stronger the toxicity of the medicament is.
Toxicity test result of epidiphenylhydrazinoketone compound on rice blast germs
| Compound (I) | Correlation coefficient | EC50(ppm) |
| WL201701 | 0.969 | 1.76 |
| WL201702 | 0.982 | 2.71 |
| WL201709 | 0.981 | 2.98 |
| WL201711 | 0.985 | 2.21 |
| WL201712 | 0.982 | 1.51 |
| WL201710 | 0.994 | 1.25 |
| WL201730 | 0.987 | 0.43 |
| WL201737 | 0.994 | 1.22 |
The correlation coefficients of the toxicity curve regression equations are all about 0.97, the fitting degree of the equations is high, and the EC50 of the compounds WL201701, WL201702, WL201709, WL201711, WL201712, WL201710, WL201730 and WL201737 are respectively 1.76ppm, 2.71ppm, 2.98ppm,2.21ppm, 1.51ppm, 1.25ppm, 0.43ppm and 1.22 ppm. Compared with the toxicity test result of rice blast fungus, the compound WL201730 has the best sterilization effect.
The synthesized phenylhydrazino ketone compound has good spectrum bactericidal activity on plant pathogenic bacteria, has small molecular weight and has value of continuous development and modification. Aiming at the situation that the inhibition effect of the rice blast fungus is close to the level of a commercial inhibitor, the rice blast fungus is developed into a novel efficient spectrum bactericide, and has wide application prospect.
The above embodiments are preferred examples of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Watch 1
Claims (4)
1. The application of the phenylhydrazino ketone compound shown in the formula (1) in inhibiting or killing fungi causing crop diseases, wherein the fungi are selected from rice blast fungus, rice sheath blight fungus, wheat scab fungus and apple ring rot fungus, the crop diseases are rice blast, rice sheath blight disease, wheat scab and apple ring rot disease,
the phenylhydrazino ketone compound shown in the formula (1) is specifically as follows:
2. the application of the phenylhydrazino ketone compound shown in the formula (1) as an agricultural bactericide,
the phenylhydrazino ketone compound shown in the formula (1) is specifically as follows:
3. use according to claim 2, characterized in that: the phenylhydrazino ketone compound shown in the formula (1) is used as an active ingredient of an agricultural bactericide, and the content of the active ingredient is more than or equal to 0.1 percent based on the total weight of the bactericide.
4. Use according to claim 2, characterized in that: when the phenylhydrazinoketone compound shown in the formula (1) is used as an active ingredient of a bactericide, the compound is mixed with a carrier or diluent allowed in a water body, a surface active agent and a surfactant to prepare various commonly used formulations, including a hydrating agent, an emulsion, an aqueous solvent and a flowable agent.
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